Amines and process for preparing them



Patented Aug.26, 1947 i I v 2,426,375 4 UNITED STATES PATENT OFFICE AMINES AND PROCESS FOR PREPARING THEM Murray Senkus, Terre Haute, Ind., assignor to Commercial Solvents Corporation, Terre Haute, Ind., a corporation of Maryland No Drawing. Application February 21, 1945 Serial No. 579,162 4 8 Claims. (Cl. 260293) l 2 My invention relates to new and useful amines. drogenation reactions occurring at lower tem- More particularly, it is concerned with amines of peratures. In general, it will be found preferable the following structural formula a to utilize catalysts that are active at lower tem- NE peratures, due to the tendency of the nitro compounds to decompose under conditions of elevated temperature and pressure.

I Hydrogen is introduced into the apparatus p in a manner such that the pressure exerted there- Wherein y be either ,p p n a subby will vary from approximately 300 to over 2000 stituted or'unsubstituted pyrrolidine or a mor- 10 pounds p r square inch. In general, however, pholine ring, and It and R represent alkyl prefer t use pressures ranging from between r p about '500 to 1000 pounds per square inch, but it This case is a continuation-in-p rt of my 0 is to be understood that other hydrogen pres- Dehdlhg Serial fi August 24, sures may be employed, their values generally 1942. being determined by the temperature used. The

Amines of they above type are re y P p hydrogenation is preferably carried out at temfIOm e Corresponding nitro 00111110111168 by sub- 1 peratures ranging from between about 30 and lecting the latter to catalytic l q id phase high 50 C., with constant agitation for a period of P es e y e t o In a a e w t is from one to four hours. Temperatures of from Procedure, the nitro comp und a yst and a 100 to 125 C., may nevertheless be utilized prosuitable solvent, such as methyl or ethyl alcohol, vided adequate precautions are taken with reare introduced into a, pressure hydrogenation aP- spect to the hydrogen pressure used. Ordinarily, paratus of conventional design, such as that deoptimum conditions in. regard to time of reacscribed at pages 29 to 45 in Adkins treatise on tion, temperature, pressure, and catalyst in any- "Reactions of Hydrogen (University of Wisgiven instance, may readily be determined b consin Press, 1937), which comprises a cylinsimple experiment.

drical steel reaction vessel fitted with a flexible When the reduction is complete, the reaction I tubing for the introduction of hydrogen under mixture is removed from the apparatus, and the pressure. The apparatus may be equipped with catalyst separated by filtration or other suita "suitable agitation means, and an electrical 30 able means. The resultingfiltrate is then disheating unit in order that the reduction may tilled at atmospheric pressure'to remove the solbeefiected under as widely varying conditions as vents, after which a liquid, such as benzene or are deemed necessary or desirable. toluene, is added to the still residue for the pur- The catalyst utilized may' be :any of several pose of removing the water formed during the rehydrogenation catalysts which are active .under duction of the nitro compound.- After all of the the operation temperatures employed, A number water is removed in this manner, the crude amine, of such hydrogenation catalysts are described in if a liquid, is purified by rectification at atmos- Ellis book on Hydrogenation of OrganicSubpheric pressure or under vacuum, or by restances, 3rd ed. (1930). In the majority of incrystallization'from' a suitable solvent, if it hapstances, however, I have found that the well- 40 pens to be a solid under ordinary conditions.

known Raney nickel catalyst usually gives the The nitro compounds employed as starting mamost satisfactory results. Numerous other hyterials for the preparation of the amines of my tlrogenation catalysts are, nevertheless, quite satinvention, may be synthesized in accordance with isfactory and will be found to be sufficiently active the procedure described in my co-pending appliunder the operating conditions employed to result. cation, U. S. Serial No. 455,931, filed August 24, in 'adeq uate yields of amines, which render the I 1942. By this procedure, a primary or secondary uselo'f such catalaystspracticable froman ecoaliphatic amine is reacted with formaldehyde nomi'cal standpoint. For example, nickel preto form the corresponding N-hydroxymethyl,

cipitated from nickel carbonataand supported on mono-, or dialkylamine which is in turn reacted infuso'rial earth (Covert. et'al, J. Amer. Chem. Soc. with an equimolecular quantity of a secondary 54, 165,1(1932) ),.or catalysts of nickel on silica nitroparaffin to produce the desired nitro comgel (Holmes and Anderson, Ind. 81 Eng. Chem. 17, pounds. The preparation of such nitro com- 280 (1925)), may also be employed. These catpounds is preferably carried out at temperatures alysts are most active at temperatures above of from between about 25-30 C. Temperatures 85'C., however, and are less desirable for hy- 9 above this range may be used, but in doing so,

Example I One hundred parts of N- (2-nitroisobutyl) piperidine were mixed with one hundred parts of methyl alcohol and 5 parts of Raney nickel catalyst after which the resulting mixture was introduced into a suitable hydrogenation apparatus and sealed. Hydrogen was then added at a. pressure of 500 pounds per square inch and at a temperature of 30-50 C. After absorption of hydrogen had substantially ceased, the. solution was re moved from the apparatus, filtered, and the filtrate distilled at atmospheric pressure to remove the methyl alcohol, Two hundred parts of benzene were then added to the still residue andthe water produced by the reduction of the nitro compound to the corresponding amine was removed as a constant boiling mixture with 'benzene, the latter being returned to the still until substantially all of the water had been separated from the crude amine. The residue was then distilled under reduced pressure and the fraction boiling at 605 C. at 6 mm.'\pressure was collected. The quantity of N-(2-aminoisobutyDpiperidine recovered amounted to a conversion of about 95%. The product had a nitrogen content of 17.86% as compared to a. calculated value of 17.94%.

Example II One hundred parts of N-(Z-nitroisobutyl) -2,5- dimethylpyrrolidin'e weremixed with one hundred parts of methyl alcohol and 5 parts of Raney nickel catalyst after which the resulting mixture was introduced into a suitable hydrogenation apparatus and sealed. Hydrogen was then added at a pressure of 500 pounds per square inch and at a temperature of 30-50 C. After absorption of hydrogen had substantially ceased, the solution was removed from, the apparatus, filtered, and the filtrate distilled at atmospheric pressure to remove the methyl alcohol. Two hundred parts of benzene were then added to the still residue and the water produced by the reduction of the nitro compound to the corresponding amine was removed as a constant boiling mixture with benzene, the latter being returned to the still until substantially all of the water had been separated from the crude amine, The residue was then distilled under reduced pressure and the fraction boiling at 59-60 C. at 3 mm. pressure was collected. The quantity of N- (2-aminoisobutyl) 2,5 dimethylpyrrolidine re-- covered amounted to a conversion of about 69%. The product had a nitrogen content of 16.42% as compared to a calculated value of 16.45%.

Example III One hundred parts of crude N-(2-nitroisobutyIl-morpholine were mixed with one hundred parts of methyl alcohol and 5 parts of Raney nickel catalyst after which the resulting mixture was introduced into a suitable hydrogenation apparatus and sealed. Hydrogen was then added at a pressure of 500 pounds per square inch and at a temperature of 30-50 C. After absorption of hydrogen had substantially ceased, the solution was removed from the apparatus, filtered, and

the filtrate distilled at atmospheric pressure to remove the methyl alcohol. Two hundred partsof benzene were then added to the still residue and the water produced by the reduction of the nitro compound to the corresponding amine was removed as a constant boiling mixture with benzene, the latter being returned to the still until substantially all of the water had been separated from-the crude amine. The residue was then distilled under reduced pressure and the fraction boiling at 68 C. at 6 mm. pressure was collected. The quantity of N-(Z-aminoisobutyl)morpholine recovered amounted to a conversion of about 59%. The product had a nitrogen content of 17.69% as compared to a calculated value of 17.72%.

The amines of the above-mentioned type are generally either colorless liquids or white solids. These amines are, as a rule, insoluble in water, but are soluble in the lower aliphatic alcohols, ether, and benzene. The majority of these amines tend to decompose on distillation at atmospheric pressure. I

The amines of my invention have been found to be useful in certain instances as intermediates for the preparation of surface active agents. They are likewise useful as intermediates in the preparation of numerous other valuable organic,

compounds and compositions. Additional uses of these products will readily occur to those skilled in the art.

My invention now having been described, what I claim is:

1. Amines of the formula RJ-CH --R1 wherein R is a member selected from the group consisting of piperidine. pyrrolidines, and morpholine, and R and R represent alkyl groups, the step which comprises subjecting the corresponding nitro compound to hydrogenation in the liquid phase in the presence of a nickel hydrogenation catalyst at a temperature not substantially in excess of C.

6. In a process for the preparation of N-(2- aminoisobutyDpiperidine, the step which comprises subjecting N-(2-nitroisobutyl) piperidine to hydrogenation in the liquid phase in the presence of a nickel hydrogenation catalyst at a temperature not substantially in excess of 125 C.

7. In a process for the preparation of N-(2- aminois'obutyl) -2,5-dimethylpyrrolidine, the step which comprises subjecting N-(2-nitroisobutyD- 2,5-dimethy1pyrrolidine to hydrogenation 1n the REFERENCES CITED liquid phase in the presence of a. nickel hydro- The following references are of record in the genation catalyst at a temperature not substanfile of this patent: tially in excess, of 125 C. 5

8. In a process for the preparation of N-(2- UNITED STATES PATENTS aminoisobutyl)morpholine, the step which com- Number Name Date prises subjecting N-(2-nitroisobutyl)morpholine 2,157,391 Vanderbilt May 9, 1939 to hydrogenation in the liquid phase in the pres- 2,157,386 Johnson May 9, 1939 ence of a nickel hydrogenation catalyst at a tem- 10. OTHER REFERENCES perature not substantially in excess of 125 C.

Chem. Abstracts, 1938, page 494 citing: Bull.

MURRAY sENKUs, Soc. Chim. (5), pages 1451-1468. 

